Wool-dyestuff of the dianthraquinonylamine series



Patented Sept. 20, 1932 UNITED STATES PATEN OFFICE,

WALTER MIEG, OFYOPLADEN, AND KURT BAMBERGER, 'onnnnnnnnnn; GERMANY,ASSIGNORS T0 GENERAL ANILINE WORKS, INC.,.0F NEW YORK, N. Y., ACORPORATION or DELAWARE WOOL-DYESTUFIE OF THE DIANTHRAQUINONYLAMINESERIES No Drawing. Application filed May 29, 1930, Serial No. 457,528,and in Germany June 7, 1929.

. wool-dyestufls of the dianthraquinonylamine.

series are obtainable by heating a compound of the probable formula:

' NH O wherein R- means hydrogen or alkyl, a: stands for hydrogen or theaminooran alkylamino group, with fuming sulfuric acid in the presenceof. boric acid and in thepresence of a small (catalytical) amount ofmercury or an oxide or a'salt thereof, such as mercuric oxide, mercuricsulfate, mercuric chloride, mercuric acetate, mercurous sulfate and thelike. i

The reaction is advantageously performed witha fuming sulfuric acidcontaining between 2050% S0 and at a temperature betweenabout 120-150(3., while applying boric acidin an amount corresponding to at least onemolecular proportion upon one greenish-blue-grey shadesof excellentfastness properties, U The products probably are aminooralkylamino-dianthraquinonylamine sulfonic acids," containing moresulfonic acid groups than the aminoaor alkylaminodianthraquinonylaminesulfonic acids hitherto known. As a result of this fact our new productsare more easily soluble in water than the known compounds, inconsequence of which they are'valuable dyestufi's for dye ing woolstrong shades. Further, they can be used in mechanical dyeing apparatus.

The following examples illustrate our invention without restricting itthereto, the

parts being by weight.

Example 1 water, containing some sulfurous acid, 200

parts of a saturated aqueous sodium chloride solution are added and thesolution is boiled until the dyestufihas separated. A dark powder isthus obtained, easily soluble in water, dissolving in strong sulfuricacid with a greenish-blue coloration, dyeing wool from an acid bathclear greyish-blue shades of excellent fastness properties. J

Example 2 10 parts of 4.4-diamino-1.1'-dianthraquinonylamine areintroduced into 150 parts of fuming sulfuric acid (27% S0 content), towhich 4 parts of boric acid and 0,2 part of mercuric oxide. have beenadded. The reaction mixture is heated to 135140 C. for

about 3 hours, while stirring, cooled, poured into 800 parts of Watercontaining some sulfurous acid, and the dyestulf is salted out by stuffof Example 1 of the German Patent No. 414,865. It dissolves in strongsulfuric acid with a dark blue coloration and dyes wool from an acidbath strong bluish-grey shades of excellent fastness properties.

Similar dyestuffs of somewhat greener shades are obtainable whenstartingwith alkylamino- 1.1 dianthraquinonylamlnes,

for example, with 4-me'thylor et'hylamino- 1.1-dianthraquinonylamine orwith 4 4- dimethylamino-1.1- dianfthraqumonylamnne and working in asimilar manner as de-- scribed in the examples.

weclaimz- 1 1 V 1. Process which comprises heating a com pound of theprobable formula wherein R meanshydrogen or alkyl, .22 stands forhydrogen or a substituent of the group consisting of the amino group andalkydamino groups, with frunmg sulfuric acid 7 in the presence of boricacid and of a small amount of a compound ofthe group consisting ofmercury, its oxides and salts. Process which comprises heatmg a compound of the probable formula v a C wherein Rn-ieans hydrogen or alkylmstands for hydrogen or a substituent of t e group consisting of theamino group and alky1- amino groups, with fuming sulfuric acid of about20+50%' SO content, at a temperature between about 120-150" 0., in thepresence of boric acid in an amount corresponding to at'least onemolecular proportion based upon onemolecular proportion of the startingmaterial employed, andin the resence ofa small amount of a compound othe group consisting of mercury, its oxides and salts,

- thraquinonylamine obtainable accordin until a test portion, afterworking up in the usual manner, is soluble in cold water.

3. Process which comprises reacting upon 4. 1 diaminol 1.1dianthraquinonylamine with fuming sulfuric acid of about 20-50% S0content, at a temperature between about 120150 0., in the presence ofboric acid in an amount corresponding to at least one.molecularproportionbased upon one molecular proportion of the startingmaterialemployed, and in the presence of a small amount of a compound;of the group consisting of mercury, its oxides and salts, until a testportion, after working up inthe usual manner, is soluble in cold water.a p a 4. Process which comprises reacting upon 10 parts by weight of4:.4-diamino-l.ldianthraquinonylamine with 150 parts by weight of fumingsulfuric acid of 27% S 08 content, containing 4 parts by weight of boricacid'and 0,2 part by weight of mercuric oxide, at a temperature of135-140 C. for about three hours, pouring the reaction mixture intowater and salting out. 7.

5. The sulfonated dianthraquinonylamine f derivatives obtainableaccording tothe process claimed in claim 1, forming dark powders, easilysoluble in water, soluble in strong sulfuric acid with dark blue tobluish-green colorations, dyeing wool from an acid bath stronggreyish-blue to greenish-blue-grey shades of excellent fastnessproperties.

6. The sulfonated dianthraquinonylamine derivatives obtainableaccordingto the process claimed in claim 2, forming dark powders, easily solublein water, soluble in strong sulfuric acid'with dark blue to bluishreencolorations, dyeing wool from an acid bath strong greyi'sh-blue togreenish-blue-grey shades of excellent fastness properties. 7, Thesulfonated dianthraquinonylamine ierivatives obtainable accordingto theprocess clalmed in claim 3, forming dark powders, easily soluble inwater,'soluble in strong sulfuric acid with dark blue to bluish-greencolorations, dyeing: wool, from an acid bath

